Gasoline fuel composition



United States Patent Ofitice 3,313,597

Patented Apr. 11, 1967 3,313,607 GASGUNE FUEL COMPOSHTION Gardner IE. Gaston, Tarentum, Pa., assignor to Gulf Research & Development Company, Pittsburgh, Pa., a corporation of Delaware i No Drawing. Filed Aug. 12, 1964, Ser. No. 389,223 20 Claims. (Cl. 4458) This invention relates to fuels and more particularly to gasoline motor fuels for high compression spark ignition engines.

In operating a spark ignition engine under normal driving conditions, there is a tendency for deposits to form in the carburetor, particularly in the throttle body area of the carburetor. While deposits may form under any driving conditions, deposits are more likely to be formed in the carburetor of an engine operating at idle speeds during a considerable period of the operating time. Such driving conditions are normally encountered in engines of automobiles used to a great extent in driving in heavy trafiic of the type encountered in city driving.

As deposits begin to build up in the throttle area of the carburetor, the clearance between the throttle plate and the body wall of the carburetor becomes increasingly less. As the clearance is reduced the amount of air pass ing the throttle plate for given amount of fuel is also reduced. As a result of a reduced amount of air, the airfuel mixture introduced into the combustion chamber is richer than it should be for satisfactory engine operation. As deposits continue to build up in the carburetor, rough engine idling is encountered and eventually the engine will stall under idling conditions.

Excessive engine stalling is, of course, a source of annoyance due to the resulting increased fuel consumption, battery wear and inconvenience of frequent restarting. Thus, carburetors in which the deposits have built up must be cleaned and in some instances must be replaced before satisfactory engine performance is obtained.

The deposits which are formed in the carburetor may be due in part to the make-up of the motor fuel which is used, but it is believed that the deposits are due, to a greater extent at least, to foreign matter introduced into the carburetor through the air intake system. The air cleaners employed in automotive engines do not appear to effectively remove these contaminants. Major contributors to air contamination are crankcase vapors formed from the crankcase, exhaust vapors, dust, smoke and the like. The problem with respect to carburetor deposits resulting from air contamination is further aggravated by the positive crankcase ventilating system which is employed in many of the current automotive engines. In engines equipped with a positive crankcase ventilating system, fumes and/or vapors from the crankcase are passed through a metering valve into the air intake system of the engine. While this system helps to cut down on fumes escaping to the atmosphere, the system adds to the problem of deposits formed in the carburetor. Deposits are encountered not only in the carburetor but also in the components of the metering valve employed in connection with the positive crankcase ventilating system.

I have found that the formation of deposits in the carburetor of a spark ignition engine and in the metering valve components of a positive crankcase ventilating system can be substantially reduced by incorporating in the gasoline motor fuel a small, deposit inhibiting amount of a combination of (1) a reaction product of lecithin and an N-aliphatic substituted polymethylene diamine and (2) an oil-soluble monocarboxylic acid salt of an N- aliphatic substituted polymethylene diamine, wherein said monocarboxylic acid contains at least 8 carbon atoms per molecule and wherein said N-aliphatic substituted polymethylene diamine in (1) and (2) hereof has the general formula:

H Rl I- (CH2) -NHz where R is an aliphatic hydrocarbon radical containing about 8 to about 30 carbon atoms and x is a number from 2 to 10. The present invention, therefore, includes a gasoline motor fuel composition that has been i. proved in the above-described fashion, and also the method of operating an internal combustion engine under conditions normally tending to form deposits in the carburetor using such improved gasoline composition as the fuel. The monocarboxylic acid salt and the lecithin-diamine product can be employed in varying proportions with respect to one another. It is generally preferred to add them in weight proportions of about 1:1 to about 2:1, but other proportions can be used, provided that each compound is present in an amount corresponding to at least about 0.001 percent by weight of the composition. Usually the compounds will be employed in weight ratios varying from about 1:5 to about 5:1.

The exact manner of functioning of the herein disclosed combinations of monocarboxylic acid salts and lecithin-diamines has not been definitely determined, and accordingly, the invention is not limited to any particular theory of operation. It may be that such combinations inhibit the formation of deposits in the carburetor by preventing their formation in the first instance. Alternatively, it may be that the herein disclosed combinations of carboxylic acid salts and lecithin-diamines function as solubilizing agents for the deposits. However, regardless of the particular mechanism by which the herein disclosed combinations function, it is clear that the components of the combination coact in a unique manner to provide substantially reduced deposits in the carburetor and metering valve components of the positive crankcase ventilating system of a spark ignition engine.

The N-aiiphatic substituted polymethylene diamine which is reacted with lecithin and the N-aliphatic substituted polymethylene diamine which is reacted with the monocarboxylic acid can be either the same or a different diamine compound. It is preferred, however, that the N-aliphatic substituted polymethylene diamine which is employed in each instance be the same or at least one having the same number of methylene groups between the nitrogen atoms. The structural formula for this class of compounds which are referred to generically as N-aliphatic substituted polymethylene diamines is as follows:

where R is an aliphatic hydrocarbon radical containing about 8 to about 30 carbon atoms and x is a number from 2 to 10.

The aliphatic group attached to the nitrogen atom is preferably a higher fatty acid residue, that is, R in the above formula is preferably an alkyl or alkenyl radical obtained from a fatty acid. Either saturated or unsaturated fatty acid residues containing from 8 to 30 carbon atoms are particularly desirable. Fatty acids providing such residues can be obtained from most naturally occurring fats and oils, such as soybean oil, coconut oil, tallow, etc. Good results are obtained when a mixture of compounds in which the aliphatic portion of the molecule varies in chain length corresponding to the various chain lengths of the aliphatic radicals provided by naturally occurring mixtures of the fatty acids. 1

While the N-aliphatic substituted polymethylene diamines can contain from 2 to 10 methylene groups in the molecule, it is generally preferred to employ those a) compounds containing 2 to 6 and especially 3 methylene groups. Thus, an especially preferred class of N-aliphatic substituted polymethylene diamines are those having the general formula:

where R is an aliphatic hydrocarbon radical containing from 8 to 30 carbon atoms. Specific examples of such N-aliphatic substituted polymethylene diamines are N- octyl trimethylene diamine, N-tetradecyl trimethylene diamine, N-tetradecenyl trimethylene diamine, N-hexadecyl trimethylene diamine, N-eicosyl trimethylene diamine, N- eicosenyl trimethylene diamine, N-docosyl trimethylene diamine, N-docosenyl trimethylene diamine, N-docosodienyl trimethylene diamine, and N-triacontanyl trimethylene diamine. Within the general class of N-aliphatic substituted trimethylene diamines which I can use, those in which the aliphatic N-substituent is an alkyl or alkenyl group containing at least 12 and preferably from 16 to 20 carbon atoms are considered to form especially effective materials. Examples of the N-aliphatic substituted trimethylene diamines which are considered to form especially effective materials are the N-dodecyl, N-hexadecyl trimethylene diamines, and especially the 18 carbon alkyl-, alkenyl-, and alkadienyl-substituted trimethylene diamines such as the N-octadecyl-, N-octadecenyl-, and N-octadecadienyl trimethylene diamines. Mixtures of N- aliphatic substituted trimethylene diamines such as are formed when the aliphatic N-substituent is derived from mixed fatty acids obtained from naturally occurring fats and oils, form highly effective materials for use in the composition of the invention. In such instances the aliphatic N-substituent is a straight-chain, monovalent hydrocarbon radical containing from 8 to 20 carbon atoms. Examples of such mixtures of N-aliphatic substituted trimethylene diamines are N-tallow trimethylene diamine, N-soya trimethylene diamine and N-coco trimethylene diamine, where the respective N-substituents are mixed alkyl and unsaturated alkyl groups derived from animal tallow c c fatty acids, soybean (C -C fatty acids, and coconut (C -C fatty acids.

The N-aliphatic substituted polymethylene diamines can be prepared by various well-known chemical procedures. According to one method, a fatty acid is treated with ammonia in the presence of a suitable solvent and catalyst to obtain the corresponding aliphatic nitrile, The nitrile is then hydrogenated under suitable conditions to obtain the corresponding primary amine. The primary amine is then treated with an aliphatic nitrile such as acrylonitrile to obtain the corresponding cyanoalkyl aliphatic amine. The cyanoalkyl aliphatic amine i then hydrogenated to obtain the N-aliphatic substituted polymethylene diamine. According to another method, a polymethylene diamine containing the desired number of methylene groups is reacted with an aliphatic chloride containing the desired number of carbon atoms. Since N-aliphatic substituted polymethylene diamines are wellknown in the art and are commercially available, no further discussion of their preparation is considered necessary. Exemplary of commercially available N-aliphatic substituted polymethylene diamines are Duomeen T and Duomeen S (products of Armour and Company) which have the general formula RNHCH CH CH NH wherein R is derived from tallow fatty acid (Duomeen T) and from soya fatty acid (Duomeen S), respectively.

The lecithin with which the N-aliphatic substituted polymethylene diamine is reacted is a commercial filtered lecithin containing a very low level of benzene-insoluble material. It can be obtained by centrifugal separation from a soybean oil that is free from foreign material. The lecithin is preferably dried so that the moisture content is less than about one percent by weight.

The lecithinxiiamine reaction product is simple to prepare. All that is required is to mix the lecithin with the diamine in the liquid phase. The mixture is then heated at about to about 150 F. until equilibrium is reached. In reacting the N-aliphatic substituted polymethylene diamine with lecithin, the lecithin is preferably diluted with a mineral oil to lower the viscosity of the lecithin which facilitates intimate contacting of the lecithin with the diamine. The diamine is added to the diluted lecithin in an amount sufficient to react with the acidic groups of the lecithin and also sufficient to neutralize any residual free fatty acids which may be present in commercial grades of lecithin. In general, the reaction mass consists of about 10 to about 99 parts by weight of lecithin and about to about 1 part by weight of the diamine or mixture of diamines. Ordinarily, however, the materials are obtained by reacting about 10 to about 80 parts by weight of lecithin with about 90 to about 20 parts by weight of the diamine. The reaction temperature is not critical so long as the temperature does not exceed the temperature at which lecithin decomposes, that is, a temperature not in excess of about 400 F. The temperature is usually maintained within the range of about 80 to about 150 F. The reaction time varies depending upon the contacting temperature and the efficiency of the contacting means. At higher temperatures, the contacting time is less than with lower temperatures. Depending upon the efficiency of the contacting means and the reaction temperature, the reaction time may vary from 15 minutes or less to 20 hours or more. In any event, contacting is continued until equilibrium is reached. Equilibrium is determined by analyzing for titratable amines. For example, there is a 12 to 15 percent loss of titratable amines as soon as the lecithin and diamine are admixed. Equilibrium is reached when the product has about 35 to about 40 percent less titratable amines than the amount originally present in the reaction mass. No definite chemical configuration or identification can be given to the reaction product. A chemical reaction does occur between the lecithin and diamine, resulting in the formation of an amide linkage as determined by spectroscopic examination. For example, at 8.85 microns, the peaks representing the molecular vibration of the diamine compound are absent from the reaction product, while at the same time the characteristic amide peaks which are absent in the diaminelecithin mixture initially are now present. More detailed information relative to the preparation and identification of the product obtained in reacting lecithin with a diamine is considered unnecessary inasmuch as the process and product are fully described in United States Pa ent No. 2,987,527, which issued in the names of Donald E. Sincroft and Endre F. Sipos on June 6, 1961.

The following is a description of a typical preparation of a .lecithin-N-coco-trimethylene diamine reaction mixture which can be used for purposes of the present invention. To 80 pounds of lecithin obtained from soybean oil, said lecithin having a moisture content less than about 0.80 percent, a benzene-insolubles value of about 0.15 percent, and an acetone-insolubles value of about 70 percent, are added 12 percent by weight of a light mineral oil diluent to reduce the viscosity of the lecithin to about 5,000 centipoises and its acetone-insolubles value to about 63.5 percent. To the mineral oil solution of lecithin, are then added 20 pounds of an N-aliphatic substituted polymethylene diamine which has the general formula wherein R is derived from fatty acids obtained by the hydrolysis of coconut oil. The reaction mass is then heated with stirring at about to F. for a period of about 16 hours, or until equilibrium is reached. The product shows about a 35 percent loss in titratable amines over the amines present in the original reaction mass. Infrared analysis shows a loss in primary and secondary amine content, with a corresponding increase in amide linkages. The product thus obtained is an oil solution of lecithin-N-coco-trimethylene diamine.

The reaction product of lecithin and the N-aliphatic substituted polymethylene diamine is employed in the gasoline motor fuel composition of my invention in small amounts ranging from about 0.001 to about 0.01 percent by weight, but preferably is Within the range of about 0.001 to about 0.004 percent by weight. Excellent results have been obtained when the lecithin-diamine product was employed in the gasoline in an amount corresponding to about 0.0015 percent by weight based on the weight of the gasoline, i.e., about 4 pounds of lecithindiamine product per 1000 barrels of gasoline. While amounts in excess of about 0.01 percent can be employed without deleteriously affecting the other properties of the composition, such larger amounts do not give significantly improved detergency characteristics in combination with the monocarboxylic acid salt of the N-aliphatic substituted polymethylene diamine. Therefore, for economic reasons, I prefer to use no more of the lecithin-diamine product than is necessary to give the desired improvement. The lecithin-diamine product is advantageously used in amounts equal in weight of the monocarboxylic acid salt of the N-aliphatic substituted polymethylene diamine.

The monocarboxylic acid with which the N-alipathic substituted polymethylene diamine is reacted to form the monocarboxylic acid salt of the N-alipathic substituted polymethylene diamine for use in the gasoline motor fuel composition of the invention can be a substantially pure acid such as oleic acid but for reasons of economy is preferably commercially available mixtures. Either saturated or unsaturated aliphatic or alicyclic mono-carboxylic acids having at least 8 carbon atoms, preferably about 8 to about 30 carbon atoms per molecule can be employed. By way of example, good results have been obtained with oil-soluble petroleum naphthenic acids. As is known, oil-soluble petroleum naphthenic acids consist principally of mixed alicyclic monocarboxylic acids con taining 8 or more carbon atoms per molecule, and are recovered by alkali washing of petroleum distillates such as kerosene, naphtha, gas oil and lubricating distillates and by subsequent acidification of the naphthenic acid salts thus obtained. Analyses of mixed naphthenic acids isolated from lubricating oils indicate that they contain from 14 to 30 carbon atoms and are monobasic acids with an average of 2.6 rings. Such acid mixtures normally possess average molecular weights ranging from about 200 to about 450. Although oil-soluble naphthenic acids derived from petroleum are preferred, the invention also includes the use of oil-soluble synthetic naphthenic acids. Examples of such acids are cyclohexyl acetic, cyclohexyl propionic and cyclohexyl stearic acids.

The invention is not limited to oil-soluble petroleum naphthenic acids, inasmuch as effective results are also obtained with combinations of the lecithin-diamine products of the class disclosed herein and oil-soluble openchain or acyclic, aliphatic monocarboxylic acids containing 8 or more preferably about 8 to about 30 carbon atoms per molecule. Specific examples of preferred acids within this class are Z-ethylhexanoic, oleic acid and stearic acid. Examples of other acids within this class are caprylic, pelargonic, nonylenic, capric, decylenic, undecylenic, lauric, .myristic, palrnitic, ricinoleic, linoleic arachidic behenic, erucic, brasidic, carnaubic, cerotic, octacosoic and melissic acids. Mixtures of long chain fatty acids containing from 8 to carbon atoms per molecule such as can be obtained from the saponification of natural fats and oils are also suitable. Examples of such acids are coconut oil (C C fatty acids), tallow (C -C fatty acids) and soybean oil (C C fatty acids).

Specific examples of the naphthenic acid and C fatty acid salts of the N-aliphatic substituted polymethylene diamines are:

N-hexadecyl-trimet-hylene diamine naphthenate, N-hexadecyl-trimethylene diamine mono-oleate, N-hexadecyl-trimethylene diamine dioleate,

N-octadecyl-trimethylene diamine naphthenate,

6 N-octadecyl-trimethylene diamine mono-oleate, N-octadecyl-trimethylene diamine dioleate, N-tallow-trimethylene diamine naphthenate, N-tallow-trimethylene diamine mono-oleate, N-tallow-trimethylene diamine dioleate, N-soya-trimethylene diamine naphthenate, N-soya-trimethylene diamine mono-oleate, N-soya-trimethylene diamine dioleate, N-coco-trimethylene diamine naphthenate, N-coco-trimethylene diamine mono-oleate and N-coco-trimethylene-diamine dioleate.

The naphthenic acid salts of the N-aliphatic substituted polymethylene diamines are economically attractive inasmuch as they can be prepared from commercial grades of naphthenic acid. The oleic acid salts are also economically attractive inasmuch as they can be prepared from a commercial grade of oleic acid known as Red oil. The oleic acid and naphthenic acid salts are particularly desirable also because of their good organophilic characteristics.

The monocarboxylic acid salt of an N-aliphatic substituted polymethylene diamine is prepared easily. All that is required is to mix the acid with the diamine in the liquid phase. An exothermic neutralization reaction takes place. The temperature is advantageously maintained between about and 230 F. The reaction product is a salt of the diamine.

In preparing the monocarboxylic acid salt of the N- aliphatic substituted polymethylene diamine, it is preferred to adrnix about 1 to about 2 moles of the acid to each mole of diamine. If more than about 2 moles of the acid is reacted with one mole of the polymethylene diamine, the reaction apparently will not go to completion. In order to avoid an excess of acid, it is usually desirable to employ slightly less than 2 moles of the acid with each mole of the diamine. Inasmuch as a diacid salt is preferred over the mono-acid salt, the amount of acid employed should be substantially more than one mole. The reaction temperature is preferably kept below about 230 F. in order to assure salt formation. If the reaction temperature exceeds about 230 F. for an extended period of time the formation of amides, rather than salts, may become excessive.

The following is a description of a typical preparation of naphthenic acid salt of N-tallow-trimethylene diamine useful for purposes of the present invention. To 27.6 grams (0.1 mol) of petroleum naphthenic acid having a molecular Weight of 276 are added at room temperature, with stirring, 20.0 grams (0.05 mol) of Duomeen T (a product of Armour and Company) which has the general formula RNI-ICH CH CH NH wherein R is derived from tallow fatty acids, said Duomeen T having a molecular weight of about 400. Upon completion of the addition of the diamine to the acid, the temperature of the mixture is about F. The reaction mass is then heated to about 210 to about 230 F. with stirring until a neutral salt is obtained. The salt thus obtained is designated as N-tallow-trimethylene diamine naphthenate.

The monocarboxylic acid salt of the N-aliphatic substituted polymethylene diamine is employed in the gasoline motor fuel composition of my invention in small amounts ranging from about 0.001 to about 0.01 percent by weight, but preferably is within the range of about 0.001 to about 0.004 percent by weight. Excellent results have been obtained when the monocarboxylic acid salt of the N-aliphatic substituted polymethylene diamine was employed in amounts corresponding to about 0.0015 percent by weight based on the weight of the gasoline, i.e., about 4 pounds of the acid salt per 1000 barrels of gasoline. While amounts in excess of about 0.01 percent can be employed without deleteriously affecting the other properties of the composition, such larger amounts do not give significantly improved detergency characteristics in combination with the reaction product of lecithin and the N-aliphatic substituted polymethylene diamine.

Therefore, for economic reasons I prefer to use no more of the monocarboxylic acid salt of the N-aliphatic substituted polymethylene diamine than is necessary to give the desired improvement. The acid salt is advantageously used in amounts equal in weight to the lecithin-diamine product.

The gasoline fuel composition to which the reaction product of lecithin with the N-aliphatic substituted polymethylene diamine and the monocarboxylic acid salt of the N-aliphatic substituted polymethylene diamine are added and in which these components perform the functions described include substantially all grades of gasoline presently being employed in automotive and internal combustion aircraft engines. Such gasolines comprise a mixture of hydrocarbons which can be obtained by at least one of the petroleum conversion processes including cracking, alkylation, aromatization, cyclization, isomerization, hydrogenation, dehydrogenation, hydroisomerization, polymerization, hydroforming, polyforming, Platforming," and combinations of two or more such processes, as well as by the Fischer-Tropsch and related processes. Thus, the term gasoline is used herein in its conventional sense to include hydrocarbons boiling in the gasoline boiling point range. While current straighbrun gasoline has octane numbers too low to qualify as the sole hydrocarbon component of gasoline fuel compositions having desirably high octane numbers, a small amount of straight-run gasoline can be blended with the hydrocarbon mixture obtained by one or more of the designated conversion processes provided the resulting mixture has a motor octane number (leaded) of at least about 85 and a research octane number (leaded) of at least about 95. A preferred gasoline fuel composition comprises a blend of hydrocarbons obtained by catalytic cracking, Platforming and alkylation processes.

In addition to the products resulting from the reaction of lecithin with an N-aliphatic substituted polymethylene diamine and a monocarboxylic acid with an N-aliphatic substituted polymethylene diamine, the gasoline motor fuel composition of my invention can contain conventional amounts of additives commonly employed in a commercial motor fuel including a tetraalkyl lead, an upper cylinder lubricant, a corrosion and oxidation inhibitor, an alkyl halide lead scavenging agent, an alcoholic anti-stalling agent, a metal deactivator, a dehazing agent, an anti-rust additive, an ignition control agent, a dye and the like. Suitable gasolines may contain up to about cubic centimeters of tetraethyl lead fluid per gallon of gasoline.

When an upper cylinder lubricant is employed it is generally used in an amount of from about 0.25 to about 0.75 percent by volume of the composition, e.g., 0.5 volume percent. This oil should be a light lubricating oil distillate, e.g., one having a viscosity at 100 F. of from about 50 to about 500 Saybolt Universal seconds, e.g., about 100 SUS. Although highly paraflinic lubricating distillates can be used, lubricating distillates obtained from Coastal or naphthenic type crude oils are preferred because of their superior solvent properties. The lubricating oil can be solvent-treated, acid-treated, or otherwise refined.

When an oxidation inhibitor is desired, any of the conventional inhibitors can be utilized. The alkylated phenols, e.g., 2,4,6-tri-tertiary-butylphenol, 2,6-di-tertiary-butyl 4-methylphenol, 2,2 bis(2-hydroxy-3-tertiarybutyl-S-methylphenyl) propane and bis(2-hydroxy-3-tertiary-butyl-S-methylphenyl)methane, because of their hydrocarbon-solubility and water-insolubiiity characteristics are preferred oxidation inhibitors. Such inhibitors when used are incorporated in the gasoline fuel composition in amounts of from about 0.001 to about 0.02 percent by weight of the composition, e.g., 0.007 weight percent.

When an ignition control agent is employed such as an organo phosphorus compound, its amount is usually expressed in terms of that which is theoretically required to convert the lead introduced into the fuel in the form of tetraalkyl lead to lead orthophosphate. While improved results can be obtained in some instances with amounts corresponding to about 0.1 times the amount theoretically required to convert the lead to lead phosphate, it is generally preferred to use an amount equal to about 0.2 to about 0.5 times the amount theoretically required to convert the lead to lead orthophosphate. In view of the fact that the amount of tetraalkyl lead in gasoline varies from one fuel to another, it is difficult to state on a weight basis the amount of a particular compound based upon the weight of the gasoline. However, once knowing the amount of tetraalkyl lead present in the gasoline, it is an easy matter to calculate the amount of the particular compound required on a weight basis. Most gasolines on the market contain between about one and about three cubic centimeters of tetraethyl lead per gallon of gasoline. Based upon such a lead content, the phosphorus compounds may be used in amounts corresponding to about 0.003 to about 0.1 percent by Weight based on the weight of the fuel. At any rate, the amount should be sufficient to incorporate between about 0.1 and about 1.0, preferably about 0.2 to about 0.5 times the amount of phosphorus required to convert the lead to lead orthophosphate. Exemplary of the organo phosphorus ignition control agents are: trimethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, dimethyl xylyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, methyl diphenyl phosphate, methyl dicresyl phosphate, ethyl dicresyl phosphate, diisopropyl phenyl phosphate, dibutyl phenyl phosphate, diisoamyl cyclohexyl phosphate, tributoxyethyl phosphate, trimethyl hosphite, triethyl phosphite, tributyl phosphite, triisooctyl phosphite, diethyl amyl phosphite, diisopropyl ethyl phosphite, dimethyl ethyl phosphite, diethyl methyl phosphine, diethyl propyl phosphine, diethyl isoamyl phosphine, tributyl phosphine and the like.

Exemplary of another specific improvement agent which I can use is N,N'-disalicylidene-1:Z-diaminopropane as a metal deactivator. The metal deactivator is generally used in small amounts of the order of about 0.0003 to about 0.001 percent by weight based on the fuel composition.

The reaction product of lecithin with the N-aliphatic substituted polymethylene diamine and the monocarboxylic acid salt of the N-aliphatic substituted polymethylene diamine can be incorporated into gasoline compositions in any convenient manner. The respective components can be separately added as such to the gasoline compositions, but it is normally preferred to employ them in the form of a concentrated solution or dispersion in a solvent such as mineral oil, gasoline, naptha, Stoddard solvent, mineral spirits, benzene, heptane, kerosene or the like. If desired, the respective components of the detergency combination can be incorporated in gasoline fuel compositions in admixture with each other, and/ or in admixture with other gasoline improvement agents, such as an antioxidant, an anti-knock agent, an ignition control additive, a dehazing agent, an anti-rust additive, a metal deactivator, an upper cylinder lubricant, a dye and the like. After addition, some circulation of the mixture will normally be desirable to expedite formation of a uniform composition, but this is not absolutely necessary.

Although the combination of the lccithin-N-aliphatic substituted polymethylene diamine and the monocarboxylic acid salt of the N-aliphatic substituted polymethylene diamine in accordance with the invention are utilized primarily as detergents in gasoline, they are additionally useful in that they impart valuable anti-rust and antiicing properties to gasoline when used in detergencyimproving amounts.

The gasoline compositions of this invention and their preparation are illustrated in detail by the following specific examples.

9 Example I A gasoline motor fuel composition in accordance with the invention is obtained by incorporating 4 pounds of the reaction product of lecithin and N-coco-trimethylene diamine (0.0015 weight percent based on the gasoline) and 4 pounds of N-tallow-trimethylene diamine naphthenate (0.0015 weight percent based on the gasoline) in 1000 barrels of gasoline. The gasoline is a blend made up of catalytically cracked gasoline, alkylate and Platformate. The gasoline motor fuel composition also contains about 3 cubic centimeters of tetraethyl lead per gallon of gasoline. Also added to 1000 barrels of the gasoline are 4 pounds (0.0015 percent by weight) of 2,6di-tertiarybutyl-4-methylphenol, 1 pound (0.0004 percent by Weight) of N,N-disalicylidene-1:Z-diaminopropane and about 48 pounds (0.018 percent by weight) (0.2 theory) of methyl diphenyl phosphate.

Example 11 Another gasoline motor fuel composition in accordance with the invention is obtained by adding 0.5 volume percent (about 0.6 percent by weight) of a light Coastal type (Texas) lubricating oil distillate to the, gasoline motor fuel composition of Example 1. Typical properties of the lubricating oil distillate are as follows:

Copper strip test, 212 F., 3 hrs Neutralization value, ASTM D 974-51 T, total acid No. 0.05

The gasoline motor fuel composition thus obtained has the following typical inspections:

Gravity, API 57.7 Sp. gr., 60/60 F 0.7479

Sulfur, L, percent 0.045 Copper strip test, 122 F., 3 hrs 1.0 Copper dish gum (ASTM D 91053T), mg./100

ml. 1 385 Existent gum, mg./100 ml. 0 Oxidation stability, min. 1440 Bromine No 20.1 Knock rating:

Motor method 90.0 Research method 98.0 TEL, ml./ gal. 2.92

Vapor Pressure, Reid, lbs 6 Distillation, gasoline:

Over point, F. 103 End point, F 402 10% evap. at F 154 50% 243 90% 331 Recovery 98.5 Residue 1.0

1 Oily.

Example III Another gasoline motor fuel composition in accordance with the invention is prepared in the manner set forth in Example I, except that a combination of (1) the reaction product of lecithin and N-coco-trimethylene diamine and (2) N-coco-trimethylene diamine naphthenate is employed as the detergent.

Example IV Another gasoline motor fuel composition in accordance with the invention is prepared in the manner set forth in Example I, except that a combination of (1) the reaction product of lecithin and N-tallow-trimethylene diamine and (2) N-tallow-trimethylene diamine naphthenate is employed as the detergent.

Example V Another gasoline mot-or fuel composition in accordance with the invention is prepared in the manner set forth in Example I, except that a combination of (1) the reaction product of lecithin and N-soya-trimethylene diamine and (2) N-soya-trimethylene diamine naphthenate is employed as the detergent.

Example VI Another gasoline motor fuel composition in accordance With the invention is prepared in the manner set forth in Example I, except that a combination of (1) the reaction product of lecithin and N-octyl-trimethylene diamine and (2) N-octyl-trimethylene diamine oleate is employed as the detergent.

Example VII Another gasoline motor fuel composition in accordance with the invention is prepared in the manner set forth in Example 1, except that a combination of 1) the reaction product of lecithin and N-tetradecyl-trimethylene diamine and (2) N-tetradecyl-trimethylene diamine oleate is employed as the detergent.

Example VIII Another gasoline motor fuel composition in accordance with the invention is prepared in the manner set forth in Example 1, except that a combination of (1) the reaction product of lecithin and N-hexadecyl-trimethylene diamine and (2) N-hexadecyl-trimethylene diamine oleate is employed as the detergent.

Example IX Another gasoline motor fuel composition in accordance with the invention is prepared in the manner set forth in Example 1, except that a combination of (1) the reaction product of lecithin and N-octadecyl-trimethylene diamine and (2) N-octadecyl-trimethylene diamine oleate is employed as the detergent.

Example X Another gasoline motor fuel composition in accordance with the invention is prepared in the manner set forth in Example 1, except that a combination of (1) the reaction product of lecithin and N-octyl-trimethylene diamine and (2) N-hexadecyl-trimethylene diamine oleate is employed as the detergent.

Example X1 Another gasoline motor fuel composition in accordance with the invention is prepared in the manner set forth in Example 1, except that a combination of (1) the reaction product of lecithin and N-hexadecyl-trimethylene diamine and (2) N-octyl-trirnethylene diamine oleate is employed as the detergent.

The gasoline motor fuel compositions described in the foregoing examples are considered illustrative only. Other lecithin-N-aliphatic substituted polymethylene diamines as well as other monocarboxylic acid salts of N-aliphatic substituted polymethylene diamines described herein can be employed in the same or equivalent proportions. Thus, for example, the reaction product of lecithin with other N-aliphatic substituted polymethylene diamines wherein the aliphatic substituent contains from 8 to 30 carbon atoms and the polymethylene consists of a chain of 2 to methylene groups can be used. The monocarboxylic acid salt can be one prepared from a monocarboxylic acid having from 8 to 30 carbon atoms and an N-aliphatic substituted polymethylene diamine wherein the aliphatic substituent contains from 8 to 30 carbon atoms and the polymethylene consists of from 2 to 10 methylene groups.

As heretofore indicated, the combination of (1) a reaction product of lecithin and an N-aliphatic substituted polymethylene diamine and (2) a monocarboxylic acid salt of an N-aliphatic substituted polymethylene diamine included by this invention produces a surprising improvement in the detergent characteristics of gasoline that normally tend to form deposits in the carburetor and in the metering valve components of a positive crankcase ventilating system. To illustrate the nature of the improvement obtained, there are presented in Table I the results obtained with engine tests made upon a gasoline motor fuel composition prepared in accordance with Example II above. In order to demonstrate the superior detergency obtained with the combination of the diamine components (1) and (2) according to the invention, there are also presented in Table I the results obtained with engine tests carried out on the base gasoline alone and the base gasoline containing each of the diamine components alone.

According to the test procedure followed, the fuel compositions to be tested are burned in a 371 cubic inch, eight cylinder, Oldsmobile engine equipped with an AC Positive Crankcase Ventilating Kit and a 2-barrel carburetor. In this test, the engine is operated for 100 cycles, each cycle consisting of 36 minutes operation at idle (650:50 rpm.) with no load and 12 minutes operation at 1800:50 rpm. with a load of 15 brake horsepower. Prior to each test, the crankcase of the engine is flushed with new lubricating oil for a period of ten minutes, a new oil filter is installed and a clean carburetor and a clean positive crankcase ventilation metering valve are installed. The test starts under the idling portion of the cycle. The jacket temperature is maintained at 175i5 F. during the test period. The air to fuel ratio is set, during idle condition, at 10.5 (10.3) to 1 at the beginning of each test. The duration of the test is 80 hours. The crankcase of the engine contains a /20W, non-detergent oil. At the conclusion of each 80-hour test, the carburetor and the positive crankcase ventilation metering valve are removed and examined. The carburetor throat is visually rated, using 0 to denote a clean rating and 22 to signify a maximum deposit rating. The metering valve is also visually rated, using 0 to denote a clean rating and 10 to signify a maximum deposit rating. The make-up of the fuels tested and the results of the engine tests are shown in Table I.

TABLE I Fuel Composition A B 0 DO) Base gasoline, Volume Percent 100 100 100 100 Ad ed:

Tetraethyl lead, BIL/Gal 3.0 3.0 3. 0 3. 0 Methyl diphcnyl phosphate,

Theory 0.2 0.2 0. 2 Coastal lubricating oil, Volume Percent 0.5 0. 5 0. 5 Reaction product of lecithin and N-cocotrimethylene diarnine, Lb./1,000 Bbl 8.0 4. 0 N-tallow-trimethylene diamine nnphthenate, Lb./1,000 Bbl. S. 0 4. 0 ,Engine Tests:

Carburetor Throat Rating 20 8 7 2 Positive crankcase Ventilation Metering Valve Rating 3 3 2 0. 8

1 Composition of E. :ample II. Rating of 0 denotes a clean condition. Rating of 22 denotes very heavy deposits.

3 Rating of 0 denotes a clean condition. Rating of 10 denotes very heavy deposits.

The data in Table I clearly demonstrate the marked superiority of a gasoline motor fuel composition of the invention (Composition D) over the base gasoline (Composition A) and the base gasoline containing each of the diamine components alone (Compositions B and C). It will be noted that while Compositions B and C gave improved carburetor ratings over the base gasoline, Composition D gave a rating that was better than would be expected from the results obtained with Compositions B and C. It will be further noted that While Compositions B and C gave little or no improvement in the positive crankcase ventilation (PCV) metering valve rating, Composition D gave a surprisingly superior improvement. These results demonstrate the excellent carburetor throat detergency and PCV metering valve detergency properties of the composition of the invention.

In order to further illustrate the detergency characteristics of a composition of the invention, a base gasoline was compared with the same gasoline containing 0.0029 percent by weight (7.5 pounds per 1000 barrels) of each of (1) a reaction product of lecithin and N-cocotrimethylene diamine and (2) N-tallow-trimethylene diamine naphthenate. The comparison was made in accordance with the Laboratory Induction System Deposit (ISD) Detergency Test. This test comprises forming a gum deposit in the test apparatus by evaporating the test fuel in the apparatus by flowing a stream of heated air counter-current to the flow of the fuel. At the completion of the test, the weight of the adhering gum is determined and compared to the reference gasoline (without additives) for an appraisal of the additives detergency action. The apparatus which is employed is described by C. C. Moore, J. L. Keller, W. L. Kent and F. S. Liggett, Evaluating Gasoline for Engine Induction System Gums, The Petroleum Engineer, vol. 27, No. 12, pages C19-30 (1955). In conducting the test, a guru deposit is formed on the walls of a steam-jacketed glass U-tube by evaporating two liters of fuel admitted to the system counter-current to a stream of preheated air. The U-tube is then washed with a number of portions of naphtha until a final wash shows no discoloration. The amount of gum adhering to the apparatus is then determined by extracting it with chemically pure acetone, evaporating the acetone extract with filtered, heated air to obtain a gum residue which is then heated in an oven /2 hour at -105 C.), cooled and weighed as noted in the published procedure. Results of the determinations using the same gasoline with and without additives are compared in order to evaluate detergency action. Table II summariazes the results obtained in the Laboratory Induction System Deposit (ISD) Detergency Test.

TABLE II L3.l)Olt1liIOIf IdSD test, weig 1t 0 a F111" Composition. deposits, mg. a

Base gasoline 41.45

Base gasoline plus (1) and (2) 13.1

1 7.5 pounds of the reaction product of lecithin and N-cocotriiucthylene diamine per 1000 barrels of gasoline.

7.5 pounds of -N-tallow trimethylene diamine naphthcnate per 1000 barrels of gasoline.

unimproved gasoline may be effectively removed by using a gasoline motor fuel composition of the invention.

As indicated hereinabove, a composition of the invention also has valuable carburetor anti-icing properties. In order to illustrate the anti-icing properties of a composition obtained in accordance with the invention, a base gasoline having a 50 percent ASTMD86 distillation point of 200 F. was compared with the same gasoline containing 0.0015 percent by Weight (4 pounds per 1000 barrels) of each of (l) a reaction product of lecithin and N-coco trimethylene diamine and (2) N-tallow-trimethylene diamine naphthenate. The comparison was made in accordance with the Mock Fuel System Test. The Mock Fuel System Test is a bench test used to appraise gasoline additives for carburetor anti-icing action. Gasoline and humidified air (both at room temperature) are fed at controlled rates to a chamber at 600 mm. Hg absolute pressure Where vaporization of the fuel refrigerates the zone to cause moisture in the air to condense and freeze. The time for ice to clog a funnel-shaped opening serves as a measure of carburetor icing tendency. The funnel-shaped opening has a i inch diameter opening at the smaller end. The tunnel is situated in the vaporizing zone upstream from the connection to a vacuum control system. When the funnel clogs with ice a rapid rise in pressure occurs and is noted on a mercury manometer connected to the vaporizing zone near the fuel and air inlets and above the funnel. Anti-icing performance is evaluated by comparing the times to clog for fuel without and with additives. Additives that increase the time to clog by 20 percent or more are effective in reducing stalls caused by carburetor icing during engine Warm-up. Table III summarizes the results obtained in the Mock Fuel System Test.

TABLE III Percent increase Composition: over base gasoline Base gasoline Base gasoline plus (1) 12.5 Base gasoline plus (2) 12.5 Base gasoline plus 50% (1) and 50% (2) 21.9

1 8 pounds of the reaction product of lecithin and N-cco-trimethylene diamine per 1000 barrels of gasoline.

2 8 pounds of N-tallow-trinlethylene diamine n-aphthenate per 1000 barrels of gasoline.

It will be noted that the gasoline composition of the invention increased the time for ice to clog the funnel by 21.9 percent.

As indicated hereinabove, a composition of the invention also has valuable anti-rust characteristics. In order to illustrate the improved anti-rust characteristics obtained in accordance With the invention gasolines containing a combination of (1) a reaction product of lecithin and an N-aliphatic substituted polymethylene diamine and (2) a monocarboxylic acid salt of an N- aliphatic substituted polymethylene diamine, the composition of Example II herein (Composition D) has been compared with a gasoline containing neither of the diamine components (1) and (2). The comparison was made in accordance With the test described in ASTM Standards on Petroleum Products and Lubricants, ASTM Designation D665-60 except that the test was conducted for a period of 4 hours at room temperature instead of 24 hours at 140 F. as suggested in the test procedure. Table IV summarizes the results obtained in the modifie-d ASTM D665-60 test when comparing a premium grade leaded gasoline With the same gasoline containing 0.0015 percent by Weight of the reaction product of locithin and N-coco-trirnethylene diamine (4 lbs/1000 bbl.) and 0.0015 percent by weight of N-tallow-trimethylene diamine naphthcnate (4 lbs/1000 bbl.).

TABLE IV Anti-rust rating after 4 hours at room temperature with the Composition composition in Distilled Water Sea Water 1 Base gasoline Heavy rust Heavy rust. Base gasoline plus and No rust No rust.

TABLE V Gasoline +4 lb./l,000 Inspections Gasoline bbl. of and 4 lb./

1,000 bbl. of

Gravity, API 57. 6 57. 7 Sp., 60l60 F 0. 7483 0. 7479 Doctor, Fed. 520.3.2 Negative Negative Sulfur, L, Percent 0. 044 0. 045 Copper Strip Test, 122 F., 3 hrs 1.0 1.0 Copper Dish Gum, Mg./ ml. 380 385 Oxidation Stability, Min 938 1, 440 Bromine No 20.0 20.1 Knock Rating:

Motor Method..- 90. 1 90. 0

Research Method 97. 9 98. 0

1 Reaction product of lecithin and N -coco-trimethylene diamine. 2 N -tallow-tr'nnethylene diamine naphthenate.

It will be noted from the data in Table V that the combination of the diamine components (1) and (2) had no deleterious affect on the physical characteristics of the gasoline. It will be noted further that the combination of the diamine components (1) and (2) had a beneficial effect on the oxygen stability of the gasoline even though the gasoline was already fairly stable.

While my invention has been described with reference to various specific examples and embodiments it Will be understood that the invention is not limited to such examples and embodiments and may be variously practiced Within the scope of the claims hereinafter made.

I claim:

1. A gasoline motor fuel composition comprising a major amount of gasoline normally tending to form deposits in the carburetor of a spark ignition engine and a small amount, sufiicient to inhibit the formation of said deposits, of a combination of (1) a reaction product of lecithin and an N-aliphatic substituted polymethylene diamine and (2) an oil-soluble hydrocarbon monocarboxylic acid salt of an N-aliphatic polymethylene diamine, Wherein said monocarboxylic acid contains at least 8 carbon atoms per molecule and wherein each of said N-aliphatic substituted polymethylene diamines in (1) and (2) hereof has the general formula:

Where R is an aliphatic hydrocarbon radical containing from 8 to 30 carbon atoms and x is a number from 2 to 10.

2. The gasoline motor fuel composition of claim 1 wherein each of said (1) a reaction product of lecithin and an N-aliphatic substituted polymethylene diamine and (2) an oil-soluble hydrocarbon monocarboxylic acid salt of an N-aliphatic substituted polymethylene diamine is present in an amount of about 0.001 to about 0.01 percent by Weight of the composition.

3. A gasoline motor fuel composition comprising a major amount of gasoline normally tending to form deposits in the carburetor of a spark ignition engine and a small amount, sufficient to inhibit the formation of said deposits, of a combination of (l) a product resulting from reacting about 10 to about 99 par-ts by weight of lecithin with about 90 to about 1 part by weight of an N-aliphatic substituted polymethylene diamine and (2) an oil-soluble hydrocarbon monocarboxylic acid salt of an N-aliphatic polymethylene diamine, wherein said monocarboxylic acid contains about 8 to about 30 carbon atoms per molecule and wherein each of said N-aliphatic substituted polymethylene diamines in (1) and (2) hereof has the general formula:

II Ri (C112) ;NH3 where R is an aliphatic hydrocarbon radical containing from 8 to 30 carbon atoms and x is a number from 2 to 10.

4. The gasoline motor fuel composition of claim 3 wherein each of said (1) a product resulting from reacting about 10 to about 99 parts by weight of lecithin with about 90 to about 1 part by weight of an N-aliphatic substituted polymethylene diamine and (2) an oil-soluble hydrocarbon monocarboxylic acid salt of an N-aliphatic substituted polymethylene diamine is present in an amount of about 0.001 to about 0.01 percent by weight of the composition.

5. A gasoline motor fuel composition comprising a major amount of gasoline normally tending to form deposits in the carburetor of a spark ignition engine and a small amount, sufficient to inhibit the formation of said deposits, of a combination of (1) a product resulting from reacting about 80 parts by Weight of lecithin with about 20 parts by weight of an N-aliphatic substituted polymethylene diamine which has the general formula wherein R is an aliphatic hydrocarbon radical derived from coconut oil fatty acids and (2) a naphthenic acid salt of an N-aliphatic polymethylene diamine which has the general formula R'NHcH CH CH NH wherein R is an aliphatic hydrocarbon radical derived from tallow fatty acids.

6. The gasoline motor fuel composition of claim 5 wherein each of said (1) a product resulting from reacting about 80 parts by weight of lecithin with about 20 parts by weight of the N-coco-trimethylene diamine and (2) a naphthenic acid salt of the N-tallowtrimethylene diamine is present in an amount of about 0.001 to about 0.01 percent by weight of the composition.

7. A gasoline motor fuel composition comprising a major amount of gasoline normally tending to form deposits in the carburetor of a spark ignition engine and a small amount, sufficient to inhibit the formation of said deposits, of a combination of (1) a reaction product of lecithin and an N-aliphatic substituted trimethylene diamine and (2) an oil-soluble hydrocarbon monocarboxylic acid salt of an N-aliphatic trimethylene diamine, wherein said monocarboxylic acid contains about 8 to about 30 carbon atoms per molecule and wherein each of said N-aliphatic substituted trimethylene diamines in (l) and (2) hereof has the general formula:

where R is an aliphatic hydrocarbon radical containing from 8 to 30 carbon atoms.

8. The gasoline motor fuel composition of claim 7 wherein each of said (1) a reaction product of lecithin and an N-aliphatic substituted trimethylene diamine and (2) an oil-soluble hydrocarbon monocarboxylic acid salt of an N-aliphatic substituted trimethylene diamine is present in an amount of about 0.001 to about 0.01 percent by weight of the composition,

9. A gasoline motor fuel composition comprising a major amount of gasoline normally tending to form deposits in the carburetor of a spark ignition engine and a small amount, sufficient to inhibit the formation of said deposits, of a combination of (l) a reaction product of lecithin and an N-aliphatic substituted trimethylene diamine and (2) an oil-soluble hydrocarbon monocarboxylic acid salt of an N-aliphatic trimethylene diamine, wherein said monocarboxylic acid contains about 8 to about 30 carbon atoms per molecule and wherein each of said N-nliphatic substituted trimethylene diamines in (l) and (2) hereof has the general formula:

where R is an aliphatic hydrocarbon radical derived from mixed fatty acids containing from about 8 to about 20 carbon atoms.

10. The gasoline motor fuel composition of claim 9 wherein said monocarboxylic acid is oleic acid.

11. The gasoline motor fuel composition of claim 9 wherein said monocarboxylic acid is a mixture of oilsoluble petroleum naphthenic acids.

12. A gasoline motor fuel composition comprising a major amount of gasoline normally tending to form deposits in the carburetor of a spark ignition engine and a small amount, sufiicient to inhibit the formation of said deposits, of a combination of (1) a reaction product of lecithin and N-coco-trimethylene diamine and (2) N- tallow-trimethylene diamine naphthenate.

13. A gasoline motor fuel composition comprising a major amount of gasoline normally tending to form deposits in the carburetor of a spark ignition engine and a small amount, sufficient to inhibit the formation of said deposits, of a combination of (l) a reaction product of lecithin and N-coco-trimethylene diamine and (2) N- coco-trimethylene diamine naphthenate.

14. A gasoline motor fuel composition comprising a major amount of gasoline normally tending to form deposits in the carburetor of a spark ignition engine and a small amount, sufiicient to inhibit the formation of said deposits, of a combination of (1) a reaction product of lecithin and N-tallow trimethylene diamine and (2) N- tallow-trirnethylene diamine naphthenate.

15. A gasoline motor fuel composition comprising a major amount of gasoline normally tending to form deposits in the carburetor of a spark ignition engine and a small amount, sufiicient to inhibit the formation of said deposits, of a combination of (l) a reaction product of lecithin and N-soya trimethylene diamine and (2) N- soya-trimethylene diamine naphthenate.

16. A gasoline motor fuel composition comprising a major amount of gasoline containing up to about 5 cubic centrimeters of tetraethyl lead per gallon of gasoline to produce a gasoline fuel composition having a motor octane number of at least about and a research octane number of at least about about 0.003 to about 0.1 percent by weight of an organo phosphorus compound, the organo phosphorus compound comprising at least about 0.1 times the theoretical amount required to convert the lead in said tetraethyl lead to lead phosphate; about 0.001 to about 0.01 percent by weight of a reaction prodduct of lecithin and N-coco-trimethylene diamine; and about 0.001 to about 0.01 percent by weight of N-tallowtrimethylene diamine napthenate.

17. A gasoline motor fuel composition comprising a major amount of gasoline containing up to about 5 cubic centimeters of tetraethyl lead per gallon of gasoline to produce a gasoline fuel composition having a motor octane number of at least about 85 and a research octane number of at least about 95; about 0.003 to about 0.1 percent by weight of methyl diphenyl phosphate, the methyl diphenyl phosphate comprising at least about 0.1 times the theoretical amount required to convert the lead in said tetraethyl lead to lead phosphate; about 0.001 to about 0.01 percent by weight of a reaction product of lecithin and N-coco-trimethylene diamine; about 0.001 to about 0.01 percent by Weight of N-talloW-trimethylene diamine naphthenate; and about 0.25 to about 0.75 percent by volume of a light lubricating distillate oil having a viscosity at 100 F. of from about 50 to about 500 Saybolt Universal seconds.

18. A gasoline motor fuel composition comprising a major amount of gasoline containing about 1 to about 3 cubic centimeters of tetraethyl lead per gallon of gasoline to produce a gasoline fuel composition having a motor octane number of at least about 85 and a research octane number of at least about 95; about 0.003 to about 0.1 percent by weight of methyl diphenyl phosphate, the methyl diphenyl phosphate comprising about 0.2 times the theoretical amount required to convert the lead in said tetraethyl lead to lead phosphate; about 0.001 to about 0.004 percent by weight of a reaction product of lecithin and N-coco-trimethylene diamine; about 0.001 to about 0.004 percent by Weight of N-taliow-trimethylene diamine naphthenate; and about 0.25 to about 0.75 percent by volume of a light lubricating distillate oil having a viscosity at 100 F. of from about 50 to about 500 Saybolt Universal seconds.

19. A gasoline motor fuel composition comprising a major amount of gasoline containing about 1 to about 3 cubic centimeters of tetraethyl lead per gallon of gasoline to produce a gasoline fuel composition having a motor octane number of at least about 85 and a research octane number of at least about 95; about 0.003 to about 0.1 percent by weight of methyl diphenyl phosphate, the methyl diphenyl phosphate comprising about 0.2 times the theoretical amount required to convert the lead in said tetraethyl lead to lead phosphate; about 0.001 to 13 about 0.004 percent by Weight of a reaction product of lecithin and N-coco-trimethylene diaminc; about 0.001 to about 0.004 percent by weight of N-talloW-trimethylene diamine naphthenate; about 0.001 to about 0.02 percent by Weight of 2,6 ditertiary-butyl-4-methylphenol; and about 0.0003 to about 0.001 percent by Weight of N,N disalicylidene-l :Z-diaminopropane.

20. A gasoline motor fuel composition comprising a major amount of gasoline containing about 3 cubic centimeters of tetraethyl lead per gallon of gasoline to produce a gasoline fuel composition having a motor octane number of about 91 and a research octane number of about 98; about 0.018 percent by weight of methyl diphenyl phosphate, the methyl diphenyl phosphate comprising about 0.2 times the theoretical amount required to convert the lead in said tetraethyl lead to lead phosphate; about 0.0015 percent by weight of a reaction product of lecithin and N-coco-trimethylene diamine; about 0.0015 percent by Weight of N-tallow-trimethylene diamine napthenate; about 0.5 percent by volume of a light lubricating distillate oil having a viscosity at 100 F. of about 100 Saybolt Universal seconds; about 0.0015 percent by Weight of 2,6-ditertiary-butyl-4-methylphenol; and about 0.0004 percent by Weight of N,N-disalicylidene-l:2-diaminopropane.

References Cited by the Examiner UNITED STATES PATENTS 2/1956 Pfohl et al. 4466 X 6/1961 Sincroft et al. 466 X 

1. A GASOLINE MOTOR FUEL COMPOSITION COMPRISING A MAJOR AMOUNT OF GASOLINE NORMALLY TENDING TO FORM DEPOSITS IN THE CARBURETOR OF A SPARK IGNITION ENGINE AND A SMALL AMOUNT, SUFFICIENT TO INHIBIT THE FORMATION OF SAID DEPOSITS, OF A COMBINATION OF (1) A REACTION PRODUCT OF LECITHIN AND AN N-ALIPHACIT SUBSTITUTED POLYMETHYLENE DIAMINE AND (2) AN OIL-SOLUBLE HYDROCARBON MONOCARBOXYLIC ACID SALT OF AN N-ALIPHATIC POLYMETHYLENE DIAMINE, WHEREIN SAID MONOCARBOXYLIC ACID CONTAINS AT LEAST 8 CARBON ATOMS PER MOLEUCLE AND WHEREIN EACH OF SAID N-ALIPHATIC SUBSTITUTED POLYMETHYLENE DIAMINES IN (1) AND (2) HEREOF HAS THE GENERAL FORMULA: R-NH-(CH2)X-NH2 WHERE R IS AN ALIPHATIC HYDROCARBON RADICAL CONTAINING FROM 8 TO 30 CARBON ATOMS AND X IS A NUMBER FROM 2 TO
 10. 17. A GASOLINE MOTOR FUEL COMPOSITION COMPRISING A MAJOR AMOUNT OF GASOLINE CONTAINING UP TO ABOUT 5 CUBIC CENTIMETERS OF TETRAETHYL LEAD PER GALLON OF GASOLINE TO PRODUCE A GASOLINE FUEL COMPOSITION HAVING A MOTOR OCTANE NUMBER OF AT LEAST ABOUT 85 AND A RESEARCH OCTANE NUMBER OF AT LEAST ABOUT 95; ABOUT 0.003 TO ABOUT 0.1 PERCENT BY WEIGHT OF METHYL DIPHENYL PHOSPHATE, THE METHYL DIPHENYL PHOSPHATE COMPRISING AT LEASST ABOUT 0.1 TIMES THE THEORETICAL AMOUNT REQUIRED TO CONVERT THE LEAD IN SAID TETRAETHYL LEAD TO LEAD PHOSPHATE; ABOUT 0.001 TO ABOUT 0.01 PERCENT BY WEIGHT OF A REACTION PRODUCT OF LECITHIN AND N-COCO-TRIMETHYLENE DIAMINE; ABOUT 0.001 TO ABOUT 0.01 PERCENT BY WEIGHT OF N-TALLOW-TRIMETHYLENE DIAMINE NAPHTHENATE; AND ABOUT 0.25 TO ABOUT 0.72 PERCENT BY VOLUME OF A LIGHT LUBRICATING DISTILLATE OIL HAVING A VISCOSITY AT 100*F. OF FROM ABOUT 50 TO ABOUT 500 SAYBOLT UNIVERSAL SECONDS. 